EP0206293A2 - Verfahren zur Herstellung von 3,5-Dichlor-2-pyridon - Google Patents
Verfahren zur Herstellung von 3,5-Dichlor-2-pyridon Download PDFInfo
- Publication number
- EP0206293A2 EP0206293A2 EP86108475A EP86108475A EP0206293A2 EP 0206293 A2 EP0206293 A2 EP 0206293A2 EP 86108475 A EP86108475 A EP 86108475A EP 86108475 A EP86108475 A EP 86108475A EP 0206293 A2 EP0206293 A2 EP 0206293A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- pyridone
- dichloro
- chlorine
- water
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 13
- ZICOPWJJZSJEDL-UHFFFAOYSA-N 3,5-dichloro-1h-pyridin-2-one Chemical compound OC1=NC=C(Cl)C=C1Cl ZICOPWJJZSJEDL-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 3
- BLHCMGRVFXRYRN-UHFFFAOYSA-N 6-hydroxynicotinic acid Chemical compound OC(=O)C1=CC=C(O)N=C1 BLHCMGRVFXRYRN-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- -1 alkaline earth metal hypochlorites Chemical class 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 3
- CNLIIAKAAMFCJG-UHFFFAOYSA-N 2,3,5-trichloropyridine Chemical compound ClC1=CN=C(Cl)C(Cl)=C1 CNLIIAKAAMFCJG-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- SZFUWUOHDRMCKD-UHFFFAOYSA-N 5-chloro-1h-pyridin-2-one Chemical compound OC1=CC=C(Cl)C=N1 SZFUWUOHDRMCKD-UHFFFAOYSA-N 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
Definitions
- the present invention relates to a new process for the preparation of 3,5-dichloro-2-pyridone, which in turn can easily be converted to 2,3,5-trichiorpyridine.
- 2,3,5-trichloropyridine is a sought-after starting material for the production of a wide range of insecticides [P.Sutter et al, J.Het.Chem.17, 493 (1980)].
- the aim of the present invention is to show a process which allows the desired 3,5-dichloro-2-pyridone to be obtained in a simple manner and in good yield and quality, starting from a cheap starting material.
- hypochlorites especially the alkali or alkaline earth metal hypochlorites, are regarded as suitable chlorine-releasing agents.
- Sodium or potassium hypochlorite is very particularly suitable.
- hypochlorites are expediently added in water in a concentration of 5 to 25%, preferably 8 to 14%.
- the chlorination agents are generally added in an excess, based on the stoichiometric ratio. In the case of hypochlorites, this excess is expediently 0 to 300%, preferably 20 to 50%.
- the excess is expediently 0 to 300%, preferably 20 to 50%.
- the process is expediently carried out in the presence of water as solvent.
- the suitable reaction temperature is expediently between 0 and 40 ° C, but a temperature of 10 ° C is preferably not exceeded.
- pH range is expediently between 7 and 12, preferably between 8 and 11 when the hypochlorites and chlorine are used as chlorination agents.
- the 3,5-dichloro-2-pyridone are removed from the reaction solution.
- the yields are generally over 70%.
- the product can be recrystallized, e.g. in water, ethyl acetate or toluene.
- the quality of the raw product is sufficient for further implementation, e.g. corresponding to U.S. Patent 4,287,347 to 2,3,5-trichloropyridine.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
Description
- Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von 3,5-Dichlor-2-pyridon, das seinerseits leicht zum 2,3,5-Trichiorpyridin umgesetzt werden kann.
- 2,3,5-Trichlorpyridin bildet ein gesuchtes Edukt für die Herstellung einer grossen Palette von Insektiziden [P.Sutter et al, J.Het.Chem.17, 493 (1980)].
- Es ist bekannt, ausgehend von 2-Pyridon durch Chlorierung das 3,5-Dichlor-2-pyridon mit einer Ausbeute von 63% herzustellen [Cava et al, J.Org.Chem23, 1614 (1958)1.
- Gemäss USSR-Patent 194 823 (Appl. 20.4.1966) ist es auch bekannt, ausgehend von 2-Pyridon durch Umsetzung mit tert-Butylhypochlorit das 3,5-Dichlor-2-pyridon im Gemisch mit 5-Chlorpyridon zu erhalten.
- Diese bekannten Verfahren haben aber den Nachteil, dass vom relativ schwer zugänglichem 2-Pyridon ausgegangen werden muß.
- Das Ziel der vorliegenden Erfindung ist es, ein Verfahren aufzuzeigen, das erlaubt, von einem günstigen Edukt ausgehend auf einfache Weise und in guter Ausbeute und Qualität zum gewünschten 3,5-Dichlor-2-pyridon zu gelangen.
- Dies wird erreicht nach einem Verfahren gemäss dem Patentanspruch 1, worin erfindungsgemäss 6-Hydroxynikotinsäure mit Chlor oder chlorabgebenden Agenzien umgesetzt wird.
- Als geeignete chlorabgebende Agenzien werden die Hypochlorite, besonders die Alkali-oder Erdalkalimetallhypochlorite angesehen. Ganz besonders geeignet ist Natrium-oder Kaliumhypochlorit.
- Die Hypochlorite werden zweckmässig gelöst in Wasser in einer Konzentration von 5 bis 25%, vorzugsweise von 8 bis 14%, zugesetzt.
- Die Chlorierungsagenzien werden allgemein in einem Ueberschuss, bezogen auf das stöchiometrische Verhältnis, zugesetzt. Dieser Ueberschuss beträgt bei den Hypochloriten zweckmässig 0 bis 300%, vorzugsweise 20 bis 50%.
- Wird Chlor verwendet, beträgt der Ueberschuss zweckmässig 0 bis 300%, vorzugsweise 20 bis 50%.
- Zweckmässig wird das Verfahren in Gegenwart von Wasser als Lösungsmittel durchgeführt.
- Die geeignete Reaktionstemperatur liegt zweckmässig zwischen 0 und 40°C, vorzugsweise wird aber eine Temperatur von 10°C nicht überschritten.
- Es wird ausserdem darauf geachtet, dass der pH-Bereich zwischen zweckmässig 7 bis 12, bei Verwendung der Hypochlorite sowie von Chlor als Chlorierungsagens vorzugsweise zwischen 8 bis 11 liegt.
- Nach beendeter Halogenierung kann auf einfache Weise, z.B. durch Filtration oder Extraktion, das 3,5-Dichlor-2-pyridon aus der Reaktionslösung entfernt werden.
- Die Ausbeuten liegen im allgemeinen über 70%.
- Gegebenenfalls kann das Produkt durch Umkristallisation, z.B. in Wasser, Ethylacetat oder Toluol, gereinigt werden. Ueberlicherweise genügt aber die Qualität des Rohproduktes zur Weiterumsetzung, z.B. entsprechend US-PS 4 287 347, zum 2,3,5-Trichlorpyridin.
- 70 g (0,5 Mol) 6-Hydroxynikotinsäure wurden in 500 ml Wasser aufgeschlämmt und anschliessend mit Natronlauge in Lösung gebracht (pH der Lösung = 10). Bei 0°C wurden langsam 100 g Chlor eingeleitet. Der pH wurde durch NaOH-Zugabe zwischen 10 und 11 gehalten.
- Nach 2 Stunden war die Chlorierung beendet. Bei pH 5 wurde der erhaltene, leicht gelbe Niederschlag abgenutscht, mit Wasser gewaschen und anschliessend unter Vakuum bei 50°C getrocknet. Man erhielt 63,5 g = 77,4% 3,5-Dichlor-2-pyridon.
- 'H-NMR (CDCI,): δ(ppm); 7,5 (d); 7,72 (d).
- 8,3 g (0,06 Mol) 6-Hydroxynikotinsäure wurden in 30 ml Wasser aufgeschlämmt und anschliessend mit Natronlauge in Lösung ge bracht (pH der Lösung = 8). Bei 5°C gab man langsam 76,5 g einer 13,6%igen Lösung von NaOCI in Wasser zu. Während der Zugabe wurde der pH zwischen 7 und 8,5 gehalten.
- Nach beendeter Reaktion wurde der entstandene, leicht gelbe Niederschlag abgenutscht, mit Wasser gewaschen und anschliessend unter Vakuum bei 50°C getrocknet.
- Man erhielt 7,0 g = 71,1% 3,5-Dichlor-2-pyridon.
- 'H-NMR (CDCI,): 3 (ppm); 7,5 (d); 7,72 (d).
Claims (6)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH2691/85A CH663957A5 (de) | 1985-06-25 | 1985-06-25 | Verfahren zur herstellung von 3,5-dichlor-2-pyridon. |
CH2691/85 | 1985-06-25 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0206293A2 true EP0206293A2 (de) | 1986-12-30 |
EP0206293A3 EP0206293A3 (en) | 1988-01-20 |
EP0206293B1 EP0206293B1 (de) | 1991-03-20 |
Family
ID=4239406
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86108475A Expired - Lifetime EP0206293B1 (de) | 1985-06-25 | 1986-06-20 | Verfahren zur Herstellung von 3,5-Dichlor-2-pyridon |
Country Status (7)
Country | Link |
---|---|
US (1) | US4681942A (de) |
EP (1) | EP0206293B1 (de) |
CA (1) | CA1265807A (de) |
CH (1) | CH663957A5 (de) |
DE (1) | DE3678209D1 (de) |
DK (1) | DK160819C (de) |
IE (1) | IE59019B1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0467308A2 (de) * | 1990-07-17 | 1992-01-22 | Lonza Ag | Verfahren zur Herstellung von 2-Hydroxy-3-halogen-5-nitropyridinen |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105541699B (zh) * | 2016-01-18 | 2018-04-17 | 浙江理工大学 | 一种3,5‑二氯‑2‑吡啶醇的制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE597974C (de) * | 1933-03-10 | 1934-06-02 | Chem Fab Von Heyden Akt Ges | Verfahren zur Darstellung von substituierten 2-Oxypyridinen |
DE2141449A1 (de) * | 1970-08-19 | 1972-02-24 | Ciba-Geigy Ag, Basel (Schweiz) | Halogen-6-hydroxy-pyridone-(2), deren Herstellung und Verwendung |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4287347A (en) * | 1980-05-12 | 1981-09-01 | Ciba-Geigy Corporation | Process for producing 2,3,5-trichloropyridine |
-
1985
- 1985-06-25 CH CH2691/85A patent/CH663957A5/de not_active IP Right Cessation
-
1986
- 1986-06-09 IE IE152886A patent/IE59019B1/en not_active IP Right Cessation
- 1986-06-17 CA CA000511731A patent/CA1265807A/en not_active Expired - Fee Related
- 1986-06-19 US US06/875,927 patent/US4681942A/en not_active Expired - Fee Related
- 1986-06-20 EP EP86108475A patent/EP0206293B1/de not_active Expired - Lifetime
- 1986-06-20 DE DE8686108475T patent/DE3678209D1/de not_active Expired - Fee Related
- 1986-06-24 DK DK296986A patent/DK160819C/da not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE597974C (de) * | 1933-03-10 | 1934-06-02 | Chem Fab Von Heyden Akt Ges | Verfahren zur Darstellung von substituierten 2-Oxypyridinen |
DE2141449A1 (de) * | 1970-08-19 | 1972-02-24 | Ciba-Geigy Ag, Basel (Schweiz) | Halogen-6-hydroxy-pyridone-(2), deren Herstellung und Verwendung |
Non-Patent Citations (1)
Title |
---|
J. Org. Chem. 23, 1614(1958) * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0467308A2 (de) * | 1990-07-17 | 1992-01-22 | Lonza Ag | Verfahren zur Herstellung von 2-Hydroxy-3-halogen-5-nitropyridinen |
EP0467308A3 (en) * | 1990-07-17 | 1992-05-20 | Lonza Ag | Process for the preparation of 2-hydroxy-3-halogen-5-nitropyridines |
Also Published As
Publication number | Publication date |
---|---|
DK160819C (da) | 1991-10-14 |
CA1265807A (en) | 1990-02-13 |
DE3678209D1 (de) | 1991-04-25 |
DK160819B (da) | 1991-04-22 |
EP0206293B1 (de) | 1991-03-20 |
DK296986A (da) | 1986-12-26 |
EP0206293A3 (en) | 1988-01-20 |
CH663957A5 (de) | 1988-01-29 |
DK296986D0 (da) | 1986-06-24 |
IE861528L (en) | 1986-12-25 |
US4681942A (en) | 1987-07-21 |
IE59019B1 (en) | 1993-12-15 |
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